Method for forming doped metal oxide films on a substrate by cyclical deposition and related semiconductor device structures

ABSTRACT

Methods for forming a doped metal oxide film on a substrate by cyclical deposition are provided. In some embodiments, methods may include contacting the substrate with a first reactant comprising a metal halide source, contacting the substrate with a second reactant comprising a hydrogenated source and contacting the substrate with a third reactant comprising an oxide source. In some embodiments, related semiconductor device structures may include a doped metal oxide film formed by cyclical deposition processes.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.62/478,471, entitled “METHOD FOR FORMING DOPED METAL OXIDE FILMS ON ASUBSTRATE BY CYCLICAL DEPOSITION AND RELATED SEMICONDUCTOR DEVICESTRUCTURES,” and filed Mar. 29, 2017, the contents of which areincorporated herein by reference.

BACKGROUND Field of the Invention

The present disclosure relates generally to methods for forming dopedmetal oxide films on a substrate by cyclical deposition and particularfor forming metal oxide films doped with at least one of silicon orgermanium. The disclosure also relates to semiconductor devicestructures including a doped metal oxide film formed by cyclicaldeposition.

Description of the Related Art

Metal oxide films, such as titanium oxide, zirconium oxide and hafniumoxide films may be utilized in the fabrication of semiconductor devicestructures. For example, titanium oxide films may be used asphotocatalyst films for fuel cell applications. In addition, titaniumoxide films may be utilized as charge collecting electrodes in dyesensitize and perovskite solar cell structures and applications.

The electrical and optical properties of metal oxide films, such astitanium oxide films, can depend on the crystal structure of the film aswell as on the doping level within the metal oxide film. Doping of metaloxide films may be achieved with a number of elements, such as, forexample niobium and tungsten, and the nature of the doping element andthe doping level may be selected to tailor the properties of the metaloxide film to a specific application. For example, titanium oxide filmsmay be utilized as transparent conducting oxides in optoelectronicapplications but the intrinsic electrical conductivity of titanium oxideis substantially lower than other traditional transparent conductiveoxides and therefore may require doping with specific elements tosignificantly improve the electrical characteristics of such titaniumoxide films.

Methods and semiconductor device structures are therefore desirable thatare able to form doped metal oxide films and particularly doped metaloxide films with a selected crystal structure and dopingcharacteristics.

SUMMARY

This summary is provided to introduce a selection of concepts in asimplified form. These concepts are described in further detail in thedetailed description of example embodiments of the disclosure below.This summary is not intended to identify key features or essentialfeatures of the claimed subject matter, nor is it intended to be used tolimit the scope of the claimed subject matter.

In some embodiments, methods for forming a doped metal oxide film on asubstrate by cyclical deposition are provided. The method may comprisecontacting the substrate with a first reactant comprising a metal halidesource, contacting the substrate with a second reactant comprising ahydrogenated source and contacting the substrate with a third reactantcomprising an oxide source.

For purposes of summarizing the invention and the advantages achievedover the prior art, certain objects and advantages of the invention havebeen described herein above. Of course, it is to be understood that notnecessarily all such objects or advantages may be achieved in accordancewith any particular embodiments of the invention. Thus, for example,those skilled in the art will recognize that the invention may beembodied or carried out in a manner that achieves or optimizes oneadvantage, or group of advantages as taught or suggested herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments will becomereadily apparent to those skilled in the art from the following detaileddescription of certain embodiments having reference to the attachedfigures, the invention not being limited to any particular embodiment(s)disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming what are regarded as embodiments of theinvention, the advantages of embodiments of the disclosure may be morereadily ascertained from the description of certain examples ofembodiments of the disclosure when read in conjunction with theaccompanying drawings, in which:

FIG. 1 is a graph showing a x-ray diffraction (XRD) scan of a silicondoped titanium oxide film formed according to the embodiments of thedisclosure;

FIG. 2 is a graph showing a combined x-ray photoelectron spectroscopy(XPS) and secondary ion mass spectroscopy (SIMS) depth profile of asilicon doped titanium oxide film formed according to the embodiments ofthe disclosure.

FIG. 3 is a graph showing a x-ray diffraction (XRD) scan of a silicondoped titanium oxide film formed according to the embodiments of thedisclosure;

FIG. 4 is a graph showing a combined x-ray photoelectron spectroscopy(XPS) and second ion mass spectroscopy (SIMS) depth profile of a silicondoped titanium oxide film formed according to the embodiment of thedisclosure;

FIGS. 5A-5C are simplified cross section views of semiconductor devicestructures including a doped metal oxide film formed according to theembodiments of the disclosure;

FIG. 6 is a scanning transmission electron microscopy (STEM) image of ananolaminate structure comprising alternating layers of substantiallycrystalline silicon doped titanium oxide and substantially amorphoussilicon doped titanium oxide; and

FIG. 7 illustrates a reaction system configured to perform certainembodiments of the disclosure.

DETAILED DESCRIPTION

The illustrations presented herein are not meant to be actual views ofany particular material, structure, or device, but are merely idealizedrepresentations that are used to describe embodiments of the disclosure.

As used herein, the term “cyclic deposition” may refer to the sequentialintroduction of precursors (reactants) into a reaction chamber todeposit a layer over a substrate and includes processing techniques suchas atomic layer deposition and cyclical chemical vapor deposition.

As used herein, the term “atomic layer deposition” (ALD) may refer to avapor deposition process in which deposition cycles, preferably aplurality of consecutive deposition cycles, are conducted in a processchamber. Typically, during each cycle the precursor is chemisorbed to adeposition surface (e.g., a substrate surface or a previously depositedunderlying surface such as material from a previous ALD cycle), forminga monolayer or sub-monolayer that does not readily react with additionalprecursor (i.e., a self-limiting reaction). Thereafter, if necessary, areactant (e.g., another precursor or reaction gas) may subsequently beintroduced into the process chamber for use in converting thechemisorbed precursor to the desired material on the deposition surface.Typically, this reactant is capable of further reaction with theprecursor. Further, purging steps may also be utilized during each cycleto remove excess precursor from the process chamber and/or remove excessreactant and/or reaction byproducts from the process chamber afterconversion of the chemisorbed precursor. Further, the term “atomic layerdeposition,” as used herein, is also meant to include processesdesignated by related terms such as, “chemical vapor atomic layerdeposition”, “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE),gas source MBE, or organometallic MBE, and chemical beam epitaxy whenperformed with alternating pulses of precursor composition(s), reactivegas, and purge (e.g., inert carrier) gas.

As used herein, the term “cyclical chemical vapor deposition” may referto any process wherein a substrate is sequentially exposed to two ormore volatile precursors, which react and/or decompose on a substrate toproduce a desired deposition.

As used herein, the term “substrate” may refer to any underlyingmaterial or materials that may be used, or upon which a device, acircuit or a film may be formed. Substrate may comprise a wafer, such assilicon wafer, glass substrate or any other type of substrate.

A number of example materials are given throughout the embodiments ofthe current disclosure, it should be noted that the chemical formulasgive for each of the example materials should not be construed aslimiting and that the non-limiting example materials given should not belimited by a given example stoichiometry.

The present disclosure includes methods for forming a doped metal oxidefilm on a substrate by a cyclical deposition process and thesemiconductor device structures themselves that include a doped metaloxide film formed by the cyclical deposition process. The methods of thedisclosure may particularly include methods for cyclical deposition ofsilicon and/or germanium doped metal oxide films comprising at least oneof titanium oxide, zirconium oxide or hafnium oxide. The disclosure mayalso include utilizing a doped metal oxide film as a component of asemiconductor device structure. The disclosure may also include methodsfor forming a doped metal oxide film with desirable electricalconductivity and desirable crystallographic properties. Examples of suchmethods and semiconductor devices structures are disclosed in furtherdetail below.

A non-limiting example embodiment of a cyclical deposition process mayinclude ALD, wherein ALD is based on typically self-limiting reactions,whereby sequential and alternating pulses of reactants are used todeposit about one atomic (or molecular) monolayer of material perdeposition cycle. The deposition conditions and precursors are typicallyselected to provide self-saturating reactions, such that an adsorbedlayer of one reactant leaves a surface termination that is non-reactivewith the gas phase reactants of the same reactant. The substrate issubsequently contacted with a different reactant that reacts with theprevious termination to enable continued deposition. Thus, each cycle ofalternated pulses typically leaves no more than about one monolayer ofthe desired material. However, as mentioned above, the skilled artisanwill recognize that in one or more ALD cycles more than one monolayer ofmaterial may be deposited, for example if some gas phase reactions occurdespite the alternating nature of the process.

In an ALD-type process for depositing a doped metal oxide film, onedeposition cycle may comprise exposing the substrate to a firstreactant, removing any unreacted first reactant and reaction byproductsfrom the reaction space, exposing the substrate to a second reactant,followed by a second removal step and exposing the substrate to a thirdreactant, followed by a third removal step. The first reactant maycomprise a metal halide source, the second reactant may comprise ahydrogenated source, and the third reactant may comprise an oxidesource.

Precursors may be separated by inert gases, such as argon (Ar) ornitrogen (N₂), to prevent gas-phase reactions between reactants andenable self-saturating surface reactions. In some embodiments, however,the substrate may be moved to separately contact a first vapor phasereactant, a second vapor phase reactant and a third vapor phasereactant. Because the reactions self-saturate, strict temperaturecontrol of the substrates and precise dosage control of the precursorsis not usually required. However, the substrate temperature ispreferably such that an incident gas species does not condense intomonolayers or multimonolayers nor thermally decompose on the surface.Surplus chemicals and reaction byproducts, if any, are removed from thesubstrate surface, such as by purging the reaction space or by movingthe substrate, before the substrate is contacted with the next reactivechemical. Undesired gaseous molecules can be effectively expelled from areaction space with the help of an inert purging gas. A vacuum pump maybe used to assist in the purging.

Reactors capable of being used to grow thin films can be used for thedeposition. Such reactors include ALD reactors, as well as CVD reactorsequipped with appropriate equipment and means for providing theprecursors. According to some embodiments, a showerhead reactor may beused.

Examples of suitable reactors that may be used include commerciallyavailable single substrate (or single wafer) deposition equipment suchas Pulsar® reactors (such as the Pulsar® 2000 and the Pulsar® 3000 andPulsar® XP ALD), and EmerALD® XP and the EmerALD® reactors, availablefrom ASM America, Inc. of Phoenix, Ariz. and ASM Europe B.V., Almere,Netherlands. Other commercially available reactors include those fromASM Japan K.K. (Tokyo, Japan) under the tradename Eagle® XP and XP8. Insome embodiments, the reactor is a spatial ALD reactor, in which thesubstrates moves or rotates during processing.

In some embodiments, a batch reactor may be used. Suitable batchreactors include, but are not limited to, Advance® 400 Series reactorscommercially available from ASM Europe B.V (Almere, Netherlands) underthe trade names A400 and A412 PLUS. In some embodiments, a verticalbatch reactor is utilized in which the boat rotates during processing.Thus, In some embodiments, the wafers rotate during processing. In otherembodiments, the batch reactor comprises a minibatch reactor configuredto accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers,4 or fewer wafers, or 2 wafers. In some embodiments in which a batchreactor is used, wafer-to-wafer non-uniformity is less than 3% (1sigma), less than 2%, less than 1% or even less than 0.5%.

The deposition processes described herein can optionally be carried outin a reactor or reaction space connected to a cluster tool. In a clustertool, because each reaction space is dedicated to one type of process,the temperature of the reaction space in each module can be keptconstant, which improves the throughput compared to a reactor in whichthe substrate is heated up to the process temperature before each run.Additionally, in a cluster tool it is possible to reduce the time topump the reaction space to the desired process pressure levels betweensubstrates.

A stand-alone reactor can be equipped with a load-lock. In that case, itis not necessary to cool down the reaction space between each run. Insome embodiments, a deposition process for depositing a thin filmcomprising a doped metal oxide film may comprise a plurality ofdeposition cycles, for example ALD cycles.

In some embodiments, the cyclical deposition processes are used to formdoped metal oxide films on a substrate and the cyclical depositionprocess may be an ALD type process. In some embodiments, the cyclicaldeposition may be a hybrid ALD/CVD or cyclical CVD process. For example,In some embodiments, the growth rate of the ALD process may be lowcompared with a CVD process. One approach to increase the growth ratemay be that of operating at a higher substrate temperature than thattypically employed in an ALD process, resulting in a chemical vapordeposition process, but still taking advantage of the sequentialintroduction of precursors, such a process may be referred to ascyclical CVD.

According to some embodiments, ALD processes are used to form dopedmetal oxide films on a substrate, such as an integrated circuitworkpiece. In some embodiments of the disclosure each ALD cyclecomprises three distinct deposition steps or phases.

In a first phase of the deposition cycle (“the metal phase”), thesubstrate surface on which deposition is desired is contacted with afirst vapor phase reactant comprising a metal precursor which chemisorbsonto the substrate surface, forming no more than about one monolayer ofreactant species on the surface of the substrate.

In addition, it should be appreciated that in some embodiments, eachcontacting step may be repeated one or more times prior to advancing onto the subsequent processing step, i.e., prior to a subsequentcontacting step or removal/purge step.

In some embodiments, a metal precursor, also referred to herein as the“metal compound” may comprise a metal halide source. In someembodiments, the first reactant may comprise a metal halide source, inparticular a transition metal halide source. The transition metal halidesource or compound may comprise at least one of the transition metalsselected from the group comprising, scandium (Sc), yttrium (Y), titanium(Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum(Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn),technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os),cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd),platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium(Cd), and mercury (Hg).

As a non-limiting example embodiment, a metal halide source, such as,e.g., titanium tetrachloride (TiCl₄), may be used as the metal halidesource in a cyclical deposition processes, such as an ALD process. Insome other embodiments, when the film is a doped zirconium oxide film ora doped hafnium oxide film, metal halides such as zirconiumtetrachloride (ZrCl₄) or hafnium tetrachloride (HfCl₄) may be used. Inother embodiments metal sources comprising metal-organic compounds oftitanium can be used. In other embodiments, metal sources comprisingmetal-organic compounds of zirconium and hafnium may be utilized. Insome embodiments, one or more metal chloride sources are used. In someembodiments, a liquid metal compound is used (liquid at approximatelyroom temperature or at approximately 20° C.).

In some embodiments, exposing the substrate to a metal halide source maycomprise pulsing the metal precursor (e.g., the titanium tetrachloride)over the substrate for a time period of between about 0.01 seconds andabout 60 seconds, between about 0.05 seconds and about 10.0 seconds,between about 0.1 seconds and about 5.0 seconds. In addition, during thepulsing of the metal halide source over the substrate the flow rate ofthe metal halide source may be less than 2000 sccm, or less than 1000sccm, or less than 500 sccm, or less than 250 sccm, or even less than150 sccm.

Excess metal halide source and reaction byproducts (if any) may beremoved from the substrate surface, e.g., by purging with an inert gas.For example, in some embodiments of the disclosure the methods mayinclude a purge cycle wherein the substrate surface is purged for a timeperiod of less than approximately 5.0 seconds. Excess metal halidesource and any reaction byproducts may be removed with the aid of avacuum generated by a pumping system.

In a second phase of the deposition cycle (“the hydrogenated phase”),the substrate is contacted with a second vapor phase reactant comprisinga hydrogenated source. In some embodiments of the disclosure, methodsmay further comprise selecting the hydrogenated source to comprise ahydrogenated silicon source and the hydrogenated silicon source mayfurther comprise at least one of silane (SiH₄), disilane (Si₂H₆),trisilane (Si₃H₈) or tetrasilane (Si₄H₁₀). In addition, the hydrogenatedsilicon source may comprise higher order silanes with the generalempirical formula Si₈H_((2x+2)). In some embodiments, the hydrogenatedsilicon source may be a cyclic silane. In some embodiments, thehydrogenated source comprises silanes without having any halides orhydrocarbons or any other ligands than hydrogen. In some embodiments ofthe disclosure, methods may further comprise selecting the hydrogenatedsource to comprise a hydrogenated germanium source and the hydrogenatedgermanium source may further comprise at least one of germane (GeH₄),digermane (Ge₂H₆), trigermane (Ge₃H₈), or tetragermane (Ge₄H₁₀). Inaddition, the hydrogenated germanium source may comprise higher germaneswith the general empirical formula Ge_(x)H_((2x+2)). In someembodiments, the hydrogenated germanium source may be a cyclic germane.In some embodiments, the hydrogenated germanium source comprisesgermanium without having any halides or hydrocarbons or any otherligands than hydrogen.

In some embodiments, exposing the substrate to the hydrogenated sourcemay comprise pulsing the hydrogenated source (e.g., disilane ordigermane) over the substrate for a time period of between 0.1 secondsand 2.0 seconds or from about 0.01 seconds to about 10 seconds or lessthan about 20 seconds, less than about 10 seconds or less than about 5seconds. During the pulsing of the hydrogenated source over thesubstrate the flow rate of the hydrogenated source may be less than 2000sccm, or less than 1000 sccm, or less than 500 sccm, or even less than100 sccm.

The second vapor phase reactant comprising a hydrogenated source mayreact with metal-containing molecules left on the substrate surface. Insome embodiments, the second phase hydrogenated source may comprise areducing agent capable of reducing the metal-containing molecules lefton the substrate surface to thereby form a metallic film comprising asilicon or germanium component. For example, the first vapor phasereactant may comprise a titanium precursor and the second vapor phasereactant may comprise a reducing agent. After the titanium precursor isintroduced into the reaction chamber and adsorb onto a substratesurface, the excess titanium precursor vapor may be pumped or purgedfrom the chamber. This process is followed by the introduction of areducing agent that reacts with the titanium precursor on the substratesurface to form a titanium metal comprising a silicon component or agermanium component and a free form of the ligand. This deposition cyclecan be repeated if needed to achieve the desired thickness of themetallic film.

Excess second source chemical and reaction byproducts, if any, may beremoved from the substrate surface, for example by a purging gas pulseand/or vacuum generated by a pumping system. Purging gas is preferablyany inert gas, such as, without limitation, argon (Ar), nitrogen (N₂) orhelium (He). A phase is generally considered to immediately followanother phase if a purge (i.e., purging gas pulse) or other reactantremoval step intervenes.

In a third phase of the deposition cycle (“the oxide phase”), thesubstrate is contacted with a third vapor phase reactant comprising anoxide source. In some embodiments of the disclosure, methods may furthercomprise selecting the oxide source to comprise at least one of ozone(O₃), an oxygen (O) radical, atomic oxygen (O), molecular oxygen (O₂),an oxygen plasma, water (H₂O), or hydrogen peroxide (H₂O₂). In certainembodiments of the disclosure the oxidizer source may comprise watervapor (H₂O).

In some embodiments, exposing the substrate to the oxide source maycomprise pulsing the oxide source (e.g., water vapor) over the substratefor a time period of between 0.1 seconds and 2.0 seconds or from about0.01 seconds to about 10 seconds or less than about 20 seconds, lessthan about 10 seconds or less than about 5 seconds. During the pulsingof the oxidizer source over the substrate the flow rate of the oxidizersource may be less than 5000 sccm, or less than 2000 sccm, or less than1000 sccm, or even less than 500 sccm.

The third vapor phase reactant comprising a oxide source may react witha film left on the substrate surface. Not to be bound by a specifictheory, in some embodiments, the third phase oxide source may comprisean oxidizing agent capable of oxidizing the film left on the substratesurface to thereby form a doped metal oxide film. In some embodiments,alternative reactions may be responsible for the formation of the dopedmetal oxide film.

Excess third source chemical and reaction byproducts, if any, may beremoved from the substrate surface, for example by a purging gas pulseand/or vacuum generated by a pumping system. Purging gas is preferablyany inert gas, such as, without limitation, argon (Ar), nitrogen (N₂) orhelium (He). A phase is generally considered to immediately followanother phase if a purge (i.e., purging gas pulse) or other reactantremoval step intervenes.

In some embodiments of the disclosure a deposition cycle may comprisealternatively and sequentially contacting the substrate with the firstreactant, followed by the second reactant, and subsequently followed bythe third reactant. The deposition cycle in which the substrate isalternatively contacted with the first vapor phase reactant (i.e., themetal halide source), the second vapor phase reactant (i.e., thehydrogenated source) and the third vapor phase reactant (i.e., the oxidesource) may be repeated two or more times until a desired thickness of adoped metal oxide film is deposited.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the second reactant and subsequently by the third reactant, the dopedmetal oxide film may be an electrical conductor. In such embodiments theelectrically conducting doped metal oxide film may have an electricalresistivity of less than approximately 200 mΩ-cm, or less thanapproximately 100 mΩ-cm, or even less than approximately 50 mΩ-cm. Insome embodiments, the doped metal oxide film has electrical resistivitymore than approximately 5 mΩ-cm, or more than approximately 10 mΩ-cm, ormore than approximately 20 mΩ-cm, or more than approximately 50 mΩ-cm,or even more than approximately 100 mΩ-cm. In such embodiments theelectrically conducting doped metal oxide film may have an electricalresistivity of less than approximately 100 mΩ-cm at a film thickness ofless than approximately 1000 nm, or less than approximately 500 nm orless than approximately 100 nm, or even less than approximately 10 nm.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the second reactant and subsequently by the third reactant the dopedmetal oxide film may have a substantially crystalline structure. As anon-limiting example embodiment FIG. 1 illustrates a graph showing the 2theta x-ray diffraction (XRD) scan of an example doped metal oxide filmformed by ALD process of the current disclosure utilizing a firstreactant, followed by a second reactant and a subsequent third reactantFor example, the XRD scan illustrated in FIG. 1 is taken from a silicondoped titanium oxide film formed by ALD utilizing titanium tetrachlorideas a first reactant, followed by disilane as a second reactant andsubsequently followed by water vapor as a third reactant at a substratetemperature of 350° C. The XRD scan illustrated in FIG. 1 indicates thatthe example silicon doped titanium oxide film formed by the methods ofthe disclosure is substantially crystalline, as indicated by the XRDpeak labelled 100. As a non-limiting example, the silicon doped titaniumoxide film illustrated in FIG. 1 has an anatase structure as denoted bythe XRD peak labelled 100.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the second reactant and subsequently by the third reactant, the dopedmetal oxide film may comprise at least one of silicon doped titaniumoxide (Ti_(1−x)Si_(x)O₂), germanium doped titanium oxide(Ti_(1−x)Ge_(x)O₂), silicon doped zirconium oxide (Zr_(1−x)Si_(x)O₂),germanium doped zirconium oxide (Zr_(1−x)Ge_(x)O₂), silicon dopedhafnium oxide (Hf_(1−x)Si_(x)O₂) or germanium doped hafnium oxide(Hf_(1−x)Ge_(x)O₂), where x is 0≤x≤1. In some embodiments of thedisclosure the doped metal oxide film, may have a general formula givenby M_(1−x)D_(x)O₂ where M is the metal, D is the dopant and wherein x isless than approximately 0.25, or x is less than approximately 0.15, or xis less than approximately 0.05, or x is less than approximately 0.03,or x is even less than approximately 0.01. In some embodiments, thedoped metal oxide film, such as M_(1−x)D_(x)O₂, is a solid solution. Insome embodiments, the doped metal oxide film, such as M_(1−x)D_(x)O₂,has crystal structure of the corresponding metal oxide, for example incase of silicon doped titanium oxide, the material has the crystalstructure of TiO₂, such as anatase. In some embodiments, the doped metaloxide film is a solid solution and is in amorphous or substantiallyamorphous phase. In some embodiments, the doped metal oxide filmcomprises a nanocomposite film. In some embodiments, the doped metaloxide film comprises a laminate film.

As a non-limiting example embodiment FIG. 2 illustrates a graph showinga combination of a x-ray photoelectron spectroscopy (XPS) scan and asecondary ion mass spectrometry (SIMS) depth profile scan of an exampledoped metal oxide film formed by the ALD process of the currentdisclosure utilizing a first reactant, followed by a second reactant anda subsequent third reactant For example, the combined XPS and SIMS depthprofile scan illustrated in FIG. 2 is taken from a silicon dopedtitanium oxide film formed by ALD utilizing titanium tetrachloride as afirst reactant, followed by disilane as a second reactant andsubsequently followed by water vapor as a third reactant at a substratetemperature of 350° C. The combination XPS and SIMS depth profile scanillustrated in FIG. 2 indicates that the example silicon doped titaniumoxide film formed by the methods of the disclosure comprisesTi_(0.97)Si_(0.03)O₂.

In some alternative embodiments of the disclosure a deposition cycle maycomprise alternatively and sequentially contacting the substrate withthe first reactant, followed by the third reactant and subsequentlyfollowed by the second reactant. The deposition cycle in which thesubstrate is alternatively contacted with the first vapor phase reactant(i.e., the metal halide source), the third vapor phase reactant (i.e.,the oxide source) and the second vapor phase reactant (i.e., thehydrogenated source) may be repeated two or more times until a desiredthickness of a doped metal oxide film is deposited.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the third reactant and subsequently by the second reactant, the dopedmetal oxide film may comprise an electrical insulator. In suchembodiments the electrically insulating doped metal oxide film may havean electrical resistivity of greater than approximately 100 mΩ-cm, orgreater than approximately 1000 mΩ-cm, or even greater thanapproximately 100000 mΩ-cm. In such embodiments the electricallyinsulating doped metal oxide film may have an electrical resistivity ofgreater than approximately 1 mΩ-cm at a film thickness of less thanapproximately 1000 nm, or less than approximately 100 nm, or even lessthan approximately 10 nm.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the third reactant and subsequently by the second reactant, the dopedmetal oxide film may have a substantially amorphous structure. As anon-limiting example embodiment FIG. 3 illustrates a graph showing the 2theta x-ray diffraction (XRD) scan of an example doped metal oxide filmformed by an ALD process of the current disclosure utilizing a firstreactant, followed by a third reactant and a subsequent second reactantFor example, the XRD scan illustrated in FIG. 3 is taken from a silicondoped titanium oxide film formed by ALD utilizing titanium tetrachlorideas a first reactant, followed by water vapor as a third reactant andsubsequently followed by disilane as a second reactant at a substratetemperature of 350° C. The XRD scan illustrated in FIG. 3 indicates thatthe example silicon doped titanium oxide film formed by the methods ofthe disclosure is substantially amorphous, as indicated by the distinctlack of any discernable XRD peaks in the XRD scan illustrated in FIG. 3.

In embodiments wherein the doped metal oxide film is formed byalternative contacting the substrate with the first reactant, followedby the third reactant and subsequently by the second reactant the dopedsilicon oxide film may comprise at least one of silicon doped titaniumoxide (Ti_(1−x)Si_(x)O₂), germanium doped titanium oxide(Ti_(1−x)Ge_(x)O₂), silicon doped zirconium oxide (Zr_(1−x)Si_(x)O₂),germanium doped zirconium oxide (Zr_(1−x)Ge_(x)O₂), silicon dopedhafnium oxide (Hf_(1−x)Si_(x)O₂), or germanium doped hafnium oxide(Hf_(1−x)Ge_(x)O₂), where x is 0≤x≤1. In some embodiments of thedisclosure the doped metal oxide film, may have a general formula givenby M_(1−x)D_(x)O₂ where M is the metal, D is the dopant and wherein x isgreater than approximately 0.05, or x is greater than approximately0.10, or x is even greater than approximately 0.15.

As a non-limiting example embodiment FIG. 4 illustrates a graph showinga combination of a x-ray photoelectron spectroscopy (XPS) scan and asecondary ion mass spectrometry (SIMS) depth profile scan of an exampledoped metal oxide film formed by the ALD processes of the currentdisclosure utilizing a first reactant, followed by a third reactant anda subsequent second reactant For example, the XPS and SIMS depth profilescan illustrated in FIG. 4 is taken from a silicon doped titanium oxidefilm formed by ALD utilizing titanium tetrachloride as a first reactant,followed by water vapor as a second reactant and subsequently followedby disilane as a third reactant at a substrate temperature of 350° C.The XPS and SIMS depth profile scan illustrated in FIG. 4 indicates thatthe example silicon doped titanium oxide film formed by the methods ofthe disclosure comprises Ti_(0.83)Si_(0.17)O₂.

Thin films comprising a doped metal oxide film deposited according tosome of the embodiments described herein may be continuous thin films.In some embodiments, the thin films comprising a doped metal oxide filmdeposited according to some of the embodiments described herein may becontinuous at a thickness below about 100 nm, below about 60 nm, belowabout 50 nm, below about 40 nm, below about 30 nm, below about 25 nm, orbelow about 20 nm, or below about 15 nm, or below about 10 nm, or belowabout 5 nm, or lower. The continuity referred to herein can bephysically continuity or electrical continuity. In some embodiments, thethickness at which a film may be physically continuous may not be thesame as the thickness at which a film is electrically continuous, andthe thickness at which a film may be electrically continuous may not bethe same as the thickness at which a film is physically continuous.

While, in some embodiments, a thin film comprising a doped metal oxidefilm deposited according to some of the embodiments described herein maybe continuous, In some embodiments, it may be desirable to form anon-continuous thin film comprising a doped metal oxide film, or a thinfilm comprising separate islands or nanoparticles comprising a dopedmetal oxide film. In some embodiments, the deposited thin filmcomprising a doped metal oxide film may comprise nanoparticles that arenot substantially physically or electrically continuous with oneanother. In some embodiments, the deposited thin film comprising a dopedmetal oxide film may comprise separate nanoparticles, or separateislands, comprising a doped metal oxide film.

It should be appreciated that, in some embodiments, the cyclicaldeposition process may comprise contacting the substrate with the firstvapor phase reactant one or more times prior to contacting the substratewith the second vapor phase reactant one or more times and subsequentlycontacting the substrate with the third vapor phase reactant one or moretimes and similarly may alternatively comprise contacting the substratewith the first vapor phase reactant one or more times prior tocontacting the substrate with the third vapor phase reactant one or moretimes and subsequently contacting the substrate with the second vaporphase reactant one or more times.

In further embodiments of the disclosure, yet further alternativepulsing sequences comprising the first reactant, the second reactant andthe third reactant may be utilized. In some embodiments of thedisclosure, a previously applied pulse of reactant may be repeatedwithin a single deposition cycle. For example, a deposition cycle maycomprise contacting the substrate with the first reactant, followed bythe second reactant, followed by repeating the first reactantsubsequently followed by the third reactant. As a non-limiting exampleof such an embodiment, the substrate may be contacted with silicontetrachloride, followed by disilane, followed by silicon tetrachloride,subsequently followed by wafer vapor. In such a non-limiting example,the doped metal oxide formed may comprise a silicon doped titanium oxideand may have a substantially crystalline structure as determined by XRDmeasurements. As a further non-limiting example, a deposition cycle maycomprise contacting the substrate with the second reactant, followed bythe first reactant, followed by repeating the second reactant andsubsequently followed by the third reactant. As a non-limiting exampleof such an embodiment, the substrate may be contacted with disilane,followed by titanium tetrachloride, followed by disilane andsubsequently followed by water vapor. In such a non-limiting example,the doped metal oxide formed may comprise a silicon doped titanium oxideand may comprise a substantially amorphous crystalline structure asdetermined by XRD measurements.

Additional embodiments of the disclosure may comprise selecting thefirst vapor phase reactant, the second vapor phase reactant and thethird vapor phase reactant to comprise non-plasma reactants, e.g., thefirst, second and third vapor phase reactants are substantially free ofionized reactive species. In some embodiments, the first, second andthird vapor phase reactants are substantially free of ionized reactivespecies, excited species or radical species. For example, the firstvapor phase reactant, the second vapor phase reactant and the thirdvapor phase reactant may comprise non-plasma reactants to preventionization damage of the underlying substrate and the associateddefects.

The cyclical deposition processes described herein, utilizing a metalhalide source, a hydrogenated source and an oxide source to form a dopedmetal oxide film, may be performed in an ALD or CVD deposition systemwith a heated substrate. For example, in some embodiments, methods maycomprise heating the substrate to temperature of between approximately80° C. and approximately 140° C., or even heating the substrate to atemperature of between approximately 80° C. and approximately 120° C. Ofcourse, the appropriate temperature window for any given cyclicaldeposition process, such as, for an ALD reaction, will depend upon thesurface termination and reactant species involved. Here, the temperaturevaries depending on the precursors being used and is generally at orbelow about 1000° C., or below about 750° C. In some embodiments, thedeposition temperature is generally at or above about 100° C. for vapordeposition processes, In some embodiments, the deposition temperature isbetween about 100° C. and about 250° C., and, in some embodiments, thedeposition temperature is between about 120° C. and about 200° C. Insome embodiments, the deposition temperature is below about 500° C.,below about 400° C., or below about 300° C. In some embodiments, thedeposition temperature can be below about 200° C., or below about 150°C., or below about 100° C., for example, if additional reactants orreducing agents, such as ones reactants or reducing agents comprisinghydrogen, are used in the process. In some instances the depositiontemperature can be above about 20° C., or above about 50° C., or aboveabout 75° C. In some embodiments, the deposition temperature can be fromabout 20° C. to about 1000° C., or from about 50° C. to about 600° C.,or from about 100° C. to about 500° C.

In some embodiments, the growth rate of the doped metal oxide film isfrom about 0.005 Å/cycle to about 5 Å/cycle, or from about 0.01 Å/cycleto about 2.0 Å/cycle. In some embodiments, the growth rate of the filmis more than about 0.05 Å/cycle, or more than about 0.1 Å/cycle, or morethan about 0.15 Å/cycle, or more than about 0.20 Å/cycle, or more thanabout 0.25 Å/cycle, or even more than about 0.3 Å/cycle. In someembodiments, the growth rate of the film is less than about 2.0 Å/cycle,or less than about 1.0 Å/cycle, or less than about 0.75 Å/cycle, or lessthan about 0.5 Å/cycle, or even less than about 0.3 Å/cycle. In someembodiments of the disclosure the growth rate of the doped metal oxidefilm may be approximately 0.5 Å/cycle.

In some embodiments, a thin film comprising a doped metal oxide maycomprise less than about 20 at-%, or less than about 10 at-%, or lessthan about 7 at-%, or less than about 5 at-%, or less than about 3 at-%,or less than about 2 at-%, or less than about 1 at-% of impurities, thatis, elements other than the desired doped metal oxide film. In someembodiments, the thin film comprising a doped metal oxide may compriseless than about 20 at-%, or less than about 10 at-%, or less than about5 at-%, or less than about 2 at-%, or less than about 1 at-% ofhydrogen. In some embodiments, the thin film comprising a doped metaloxide may comprise less than about 10 at-%, or less than about 5 at-%,or less than about 2 at-%, or less than about 1 at-%, or less than about0.5 at-% of carbon. In some embodiments, the thin film comprising adoped metal oxide may comprise less than about 5 at-%, or less thanabout 2 at-%, or less than about 1 at-%, or less than about 0.5 at-%, orless than about 0.2 at-% of nitrogen. In some embodiments, the thin filmcomprising a doped metal oxide may comprise less than about 75 at-%, orless than about 70 at-%, or less than about 68 at-%, or more than about40 at-%, or more than about 50 at-%, or more than about 60 at-%, or morethan about 64% of oxygen. In some embodiments, the doped metal oxidefilm may comprises from about 40 at-% to about 80 at-%, or from about 55at-% to about 75 at-%, or from about 60 at-% to about 72% of oxygen, orfrom about 66 to about 67% of oxygen. In some embodiments, the dopedmetal oxide film may comprise the dopant (Si or Ge) from about 0 at-% toabout 40 at-%, or from about 1 at-% to about 25 at-%, or from about 2at-% to about 15%, or from about 5 at-% to about 15% of silicon orgermanium. In some embodiments, the doped metal oxide film may comprisefrom the dopant (Si or Ge) more than about 1 at-%, or more than about 2at-%, or more than about 5 at-%, or more than about 8 at-%, or more thanabout 10 at-%, or more than about 15 at-% of silicon or germanium. Insome embodiments, the doped metal oxide film may comprises from the saidmetal from about 20 at-% to about 75 at-%, or from about 30 at-% toabout 70 at-%, or from about 40 at-% to about 67%, or from about 50 at-%to about 65% of the said metal. In some embodiments, the doped metaloxide film may comprises from the said metal more than about 20 at-%, ormore than about 30 at-%, or more than about 40 at-%, or more than about50 at-%, or more than about 55 at-%, or more than about 60 at-% of thesaid metal (titanium, hafnium or zirconium, and in particularembodiments titanium).

In some embodiments, the doped metal oxide films may be deposited onthree-dimensional structures. In some embodiments, the step coverage ofthe doped metal oxide film may be equal to or greater than about 50%, orgreater than about 80%, or greater than about 90%, or about 95%, orabout 98%, or about 99%, or greater in structures having aspect ratios(height/width) of more than about 2, or more than about 5, or more thanabout 10, or more than about 25, or more than about 50, or more thanabout 100.

In some embodiments, the doped metal oxide films has a RMS (root meansquare) roughness, for example as measured by AFM (atomic forcemicroscopy), of less than approximately 10 nm, or less thanapproximately 5 nm, or less than approximately 2 nm, or less thanapproximately 1 nm, or less than approximately 0.5 nm, or less thanapproximately 0.35 nm, or less than approximately 0.3 nm, or less thanapproximately 0.25 nm, or even less than approximately 0.2 nm.

In some embodiments, the doped metal oxide film etch rate, such as thewet etch rate (WER) or the dry etch rate (DER), and the selectivity toother materials can be tuned by tuning the film properties by, forexample, changing the pulsing order in a desired manner. In someembodiments, the doped metal oxide film may have etch selectivitytowards pure metal oxide films or other metal oxide films. In otherembodiments the doped metal oxide film has etch selectivity towards puresilicon dioxide films. In yet other embodiments the doped metal oxidefilm may have etch selectivity towards other film types, such as siliconnitrides, or carbides, or mixtures thereof, metal nitrides, or carbides,or mixtures thereof. In some embodiments, the etch rate of the dopedmetal oxide film is more or less than pure metal oxide film. In someembodiments, the etch rate of the doped metal oxide films is more orless than the pure silicon dioxide film. In some embodiments, at leasttwo or more different doped metal oxide films having substantiallydifferent etch rates (and corresponding etch selectivity) are deposited,for example in a process flow comprising multiple patterning, bychanging the pulsing order and/or pulsing ratio in desired manner.

In some embodiments, the doped metal oxide film has tunable opticalproperties, such as refractive index (n) and/or extinction coefficient(k). In some embodiments, n is less than approximately 1.7, or n is lessthan approximately 1.9, or n is less than approximately 2.1, or n isless than approximately 2.3, or n is less than approximately 2.5. Insome embodiments, n is more than approximately 1.9, or n is more thanapproximately 2.0, or n is more than approximately 2.1, or n is morethan approximately 2.2, or n is more than approximately 2.3. In someembodiments, at least two or more optically different doped metal oxidefilms are deposited, for example in a process flow comprising multiplepatterning, by changing the pulsing order and/or pulsing ratio indesired manner.

In some embodiments, the deposited doped metal oxide film may besubjected to a treatment process after deposition. In some embodiments,this treatment process may, for example, enhance the conductivity orcontinuity of the deposited film comprising a doped metal oxide. In someembodiments, a treatment process may comprise, for example an annealprocess. In some embodiments, the film comprising a doped metal oxidemay be annealed in an atmosphere comprising vacuum or one or moreannealing gases, for example a reducing gas such as reducing gascomprising hydrogen.

The doped metal oxide films formed by the cyclical deposition processesdisclosed herein can be utilized in a variety of contexts, such as inthe formation of semiconductor device structures.

One of skill in the art will recognize that the processes describedherein are applicable to many contexts, including fabrication of diodesincluding light emitting diodes and transistors including planar devicesas well as multiple gate transistors, such as FinFETs. As a non-limitingexample, a transistor structure may comprise a channel materialcomprising a doped metal oxide (e.g., Ti_(1−x)Si_(x)O₂). In greaterdetail and with reference to FIG. 5A, a semiconductor device structuremay comprise a transistor structure and may further comprise a substrate500, a source region 502, and a drain region 504 with a conductive dopedmetal oxide 506, formed by the methods of the disclosure, disposedbetween the source region 502 and the drain region 504. The exampletransistor structure may also comprise an insulator 508 disposed abovethe conductive doped metal oxide layer 506 and in addition a gatestructure 510 disposed above the insulator 508.

As a further non-limiting example, a device structure may comprise asolar cell device wherein the solar cell device comprises a transparentconductive oxide comprising a doped metal oxide (e.g.,Ti_(1−x)Si_(x)O₂). In greater detail, and with reference to FIG. 5B, asemiconductor device structure may comprise a solar cell structure andmay further comprise a backside contact 512 in contact with asemiconductor 514. The solar cell structure of FIG. 5B may also comprisea conductive doped metal oxide 516 disposed above the semiconductor 514,the conductive doped metal oxide 516 being formed by the methods of thedisclosure.

In further embodiments of the disclosure, the doped metal oxide films ofthe current disclosure may be utilized as useful layers in thefabrication of semiconductor device structures. As non-limiting exampleembodiments, the doped metal oxide films of the current disclosure maybe utilized as sacrificial films, or hard masks for applications relatedto multiple patterning applications, such as, for example, double orquadruple patterning applications. For example, the embodiments of thedisclosure may allow for the formation of doped metal oxide films withadjustable (i.e., tunable) properties, including, but not limited to,optical properties, roughness, electrical resistivity, crystallinity andetch rate. Therefore, the doped metal oxide films formed by the methodsof the current disclosure may be suitable for lithography/patterningrelated applications, such as, for example, multiple patterningapplications. Therefore, some embodiments of the disclosure may comprisea partially fabricated device structure comprising a masking structureconfigured for subsequent patterning of an underlying layer, the maskingstructure comprising a doped metal oxide formed by the methods of thecurrent disclosure. In greater detail and with reference to FIG. 5C apartially fabricated device structure as illustrated in FIG. 5C maycomprise a substrate 518. Disposed over the substrate 518 may be aresist or hard-mask 520, formed by photolithography methods. Disposedover the resist or hard-mask 522 may be a doped metal oxide formed bythe methods of the disclosure.

In some embodiments of the disclosure, a device structure may compriseone or more alternating layers of doped metal oxide wherein the dopedmetal oxide film formed may comprise alternating layers of doped metaloxide with differing electrical and structural properties. As anon-limiting example embodiment, the methods of the disclosure may forma doped metal oxide structure comprising alternating layers ofsubstantially crystalline doped metal oxide and substantially amorphousdoped metal oxide. In additional embodiments of the disclosure, methodsmay comprise forming a doped metal oxide structure comprisingalternating layers of doped metal oxides comprising differing electricalconductivities.

FIG. 6 illustrates a non-limiting example embodiment of the currentdisclosure which shows an aberration corrected scanning transmissionelectron microscopy (STEM) image of a nanolaminate structure comprisingalternating layers of substantially crystalline silicon doped titaniumoxide and substantially amorphous silicon doped titanium oxide. In someembodiments, the doped metal oxide film is transparent or substantiallytransparent to visible light. In some embodiments, the doped metal oxidefilm is crystalline and is electrically conductive. In some embodiments,the doped metal oxide film is substantially amorphous, for example ascharacterized by XRD, and is insulating. In some embodiments, the dopedmetal oxide films electrical and optical properties can be tuned.

In greater detail, FIG. 6 illustrates a substrate 500 comprising silicondioxide (SiO₂), substantially amorphous silicon doped titanium oxidelayers 502 and substantially crystalline silicon doped titanium oxidelayer 504. The layer denoted as 506 comprises a layer of carbon utilizedas part of the measurement technique. The substantially amorphoussilicon doped titanium oxide layers 502 are formed by alternately andsequentially contacting the substrate with titanium tetrachloride,followed by water, followed subsequently by disilane, whereas thesubstantially crystalline silicon doped titanium oxide layer 504 isformed by alternately and sequentially contacting the substrate withtitanium tetrachloride, followed by disilane, followed subsequently bywater vapor. As a non-limiting example embodiment of the disclosure, ananolaminate structure as described herein, comprising alternating layerof substantially crystalline and substantially amorphous layers of dopedmetal oxides (e.g., Ti_(1−x)Si_(x)O₂) may comprise the channel region ina transistor device structure.

Embodiments of the disclosure may also include a reaction systemconfigured for forming the doped metal oxide films of the presentdisclosure. In more detail, FIG. 7 schematically illustrates a reactionsystem 700 including a reaction chamber 702 that further includesmechanism for retaining a substrate (not shown) under predeterminedpressure, temperature, and ambient conditions, and for selectivelyexposing the substrate to various gases. A precursor reactant source 704may be coupled by conduits or other appropriate means 704A to thereaction chamber 702, and may further couple to a manifold, valvecontrol system, mass flow control system, or mechanism to control agaseous precursor originating from the precursor reactant source 704. Aprecursor (not shown) supplied by the precursor reactant source 704 maybe liquid or solid under room temperature and standard atmosphericpressure conditions. Such a precursor may be vaporized within a reactantsource vacuum vessel, which may be maintained at or above a vaporizingtemperature within a precursor source chamber. In such embodiments, thevaporized precursor may be transported with a carrier gas (e.g., aninactive or inert gas) and then fed into the reaction chamber 702through conduit 704A. In other embodiments, the precursor may be a vaporunder standard conditions. In such embodiments, the precursor does notneed to be vaporized and may not require a carrier gas. For example, inone embodiment the precursor may be stored in a gas cylinder. Thereaction system 700 may also include additional precursor reactantsources, such as precursor reactant sources 706 and 708 which may alsobe couple to the reaction chamber by conduits 706A and 708A as describedabove.

A purge gas source 710 may also be coupled to the reaction chamber 702via conduits 710A, and selectively supplies various inert or noble gasesto the reaction chamber 702 to assist with the removal of precursor gasor waste gasses from the reaction chamber. The various inert or noblegasses that may be supplied may originate from a solid, liquid or storedgaseous form.

The reaction system 700 of FIG. 7, may also comprise a system operationand control mechanism 712 that provides electronic circuitry andmechanical components to selectively operate valves, manifolds, pumpsand other equipment included in the reaction system 700. Such circuitryand components operate to introduce precursors, purge gasses from therespective precursor sources 704, 706, 708, and purge gas source 710.The system operation and control mechanism 712 also controls timing ofgas pulse sequences, temperature of the substrate and reaction chamber,and pressure of the reaction chamber and various other operationsnecessary to provide proper operation of the reaction system 700. Theoperation and control mechanism 712 can include control software andelectrically or pneumatically controlled valves to control flow ofprecursors, reactants and purge gasses into and out of the reactionchamber 702. The control system can include modules such as a softwareor hardware component, e.g., a FPGA or ASIC, which performs certaintasks. A module can advantageously be configured to reside on theaddressable storage medium of the control system and be configured toexecute one or more processes.

Those of skill in the relevant arts appreciate that other configurationsof the present reaction system are possible, including different numberand kind of precursor reactant sources and purge gas sources. Further,such persons will also appreciate that there are many arrangements ofvalves, conduits, precursor sources, purge gas sources that may be usedto accomplish the goal of selectively feeding gasses into reactionchamber 702. Further, as a schematic representation of a reactionsystem, many components have been omitted for simplicity ofillustration, and such components may include, for example, variousvalves, manifolds, purifiers, heaters, containers, vents, and/orbypasses.

The example embodiments of the disclosure described above do not limitthe scope of the invention, since these embodiments are merely examplesof the embodiments of the invention, which is defined by the appendedclaims and their legal equivalents. Any equivalent embodiments areintended to be within the scope of this invention. Indeed, variousmodifications of the disclosure, in addition to those shown anddescribed herein, such as alternative useful combination of the elementsdescribed, may become apparent to those skilled in the art from thedescription. Such modifications and embodiments are also intended tofall within the scope of the appended claims.

What is claimed is:
 1. A method for forming a doped metal oxide film ona substrate by cyclical deposition, the method comprising: contactingthe substrate with a first reactant comprising a metal halide source;contacting the substrate with a second reactant comprising ahydrogenated source, wherein the hydrogenated source is a dopantprecursor for the doped metal oxide film; and contacting the substratewith a third reactant comprising an oxide source; wherein the dopedmetal oxide film comprises between 2 atomic percent and 15 atomicpercent of dopant.
 2. The method of claim 1, wherein the cyclicaldeposition comprises atomic layer deposition.
 3. The method of claim 1,further comprising selecting the metal halide source to comprise atleast one of titanium tetrachloride (TiCl₄) and zirconium tetrachloride(ZrCl₄).
 4. The method of claim 1, further comprising selecting thehydrogenated source to comprise at least one of a hydrogenated siliconsource, or a hydrogenated germanium source.
 5. The method of claim 4,further comprising selecting the hydrogenated silicon source to compriseat least one of silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), ortetrasilane (Si₄H₁₀).
 6. The method of claim 5, further comprisingselecting the hydrogenated silicon source to comprise disilane (Si₂H₆).7. The method of claim 4, further comprising selecting the hydrogenatedgermanium source to comprise at least one of germane (GeH₄), digermane(Ge₂H₆), trigermane (Ge₃H₈), or tetragermane (Ge₄H₁₀).
 8. The method ofclaim 1, further comprising selecting the oxide source to comprise atleast one of ozone (O₃), an oxygen (O) radical, atomic oxygen (O),molecular oxygen (O₂), an oxygen plasma, water (H₂O), or hydrogenperoxide (H₂O₂).
 9. The method of claim 8, further comprising selectingthe oxide source to comprise water vapor (H₂O).
 10. The method of claim1, wherein the method comprises at least one deposition cycle in whichthe substrate is alternately and sequentially contacted with the firstreactant, the third reactant and the second reactant.
 11. The method ofclaim 10, wherein the deposition cycle is repeated two or more times.12. The method of claim 10, further comprising forming the doped metaloxide film to have an electrical resistivity of greater than 1000 me-cm.13. The method of claim 10, further comprising forming the doped metaloxide metal film to have a substantially amorphous structure.
 14. Themethod of claim 1, further comprising heating the substrate to atemperature of less than about 350° C.
 15. The method of claim 1,further comprising selecting the doped metal oxide film to comprise atleast one of silicon doped titanium oxide (Ti_(1−x)Si_(x)O₂), germaniumdoped titanium oxide (Ti_(1−x)Ge_(x)O₂), silicon doped zirconium oxide(Zr_(1−x)Si_(x)O₂), germanium doped zirconium oxide (Zr_(1−x)Ge_(x)O₂),silicon doped hafnium oxide (Hf_(1−x)Si_(x)O₂), or germanium dopedhafnium oxide (Hf_(1−x)Ge_(x)O₂).